CN103443712A - Magenta toner - Google Patents

Magenta toner Download PDF

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Publication number
CN103443712A
CN103443712A CN2012800138843A CN201280013884A CN103443712A CN 103443712 A CN103443712 A CN 103443712A CN 2012800138843 A CN2012800138843 A CN 2012800138843A CN 201280013884 A CN201280013884 A CN 201280013884A CN 103443712 A CN103443712 A CN 103443712A
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Prior art keywords
toner
particle
mean
formula
resin
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Inventor
谷泰
高桥薫
仲野正雄
氏房孝行
新藤太一
斋藤惠
村井康亮
井上圭
宫崎健
广濑雅史
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Canon Inc
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Canon Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • G03G9/0914—Acridine; Azine; Oxazine; Thiazine-;(Xanthene-) dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G03G9/08708—Copolymers of styrene
    • G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid

Abstract

There is provided a magenta toner having spectral reflection characteristics, such as high color developability and transparency, and high lightfastness. The magenta toner contains at least a water-insoluble xanthene dye compound having a specific structure and a binder resin.

Description

Magenta toner
Technical field
The present invention relates to the magenta toner used in image forming methods such as electrophotography, static dump and toner injection method.
Background technology
In panchromatic digital copier and printer, the colorant in developer affects image quality significantly.Therefore, in pigment is used as to the situation of colorant, need to pulverizes fully pigment and pigment is scattered in medium equably.
In color toner, magenta toner comprises quinacridone pigment, thioindigo pigment, perylene dye, pyrrolo-pyrrole-dione (diketopyrrolopyrrole) pigment, xanthene dye and monoazo dyes and pigment by the known embodiment of colorant.
In these compounds, xanthene dye is as excellent colorant and have spectral characteristics such as high-color rendering and the transparency.Therefore, xanthene dye is suitable for various application (referring to patent documentation 1 and 2).
The quoted passage list
Patent documentation
Patent documentation 1 Japanese Patent Laid-Open 2009-080478 communique
Patent documentation 2 Japanese patent laid-open 5-034980 communiques
Summary of the invention
the problem that invention will solve
Pigment is being pulverized so that in improving the situation such as colouring power (tinting power) and the spectral characteristic such as transparent of pigment, applying and causing the growth of crystal and transformation etc. with contacting of solvent of dispersion steps and heat in production stage subsequently, adversely cause problems such as colouring power and transparency reduction thus.
Simultaneously, the xanthene dye described in patent documentation 1 and 2 does not have sufficient photostability usually.In addition, xanthene dye as magenta toner with in the situation of colorant, the compatibility of resin glue is not reached to gratifying level.
Therefore, aspect of the present invention has solved the problems referred to above.
That is, aspect of the present invention provides the magenta toner with excellent colour rendering and transparency etc. and high-light-fastness.
for the scheme of dealing with problems
The present invention is described below.
That is, aspect of the present invention provides and at least comprises by the water-insoluble dye composition of formula (1) expression and the magenta toner of resin glue:
Formula (1)
Figure BDA0000383456350000021
[in its Chinese style (1), R 1, R 5, R 6and R 10mean independently of one another alkyl; R 3and R 8mean independently of one another hydrogen atom, alkyl, alkoxy or aryloxy group; And R 2, R 4, R 7and R 9mean independently of one another hydrogen atom or the acylamino-meaned by formula (2), condition is R 2, R 4, R 7and R 9one of at least mean the acylamino-meaned by formula (2):
Formula (2)
Figure BDA0000383456350000031
(in its Chinese style (2), R 11mean alkyl, naphthenic base, aryl, aralkyl, thiazolinyl or heterocyclic radical; And * means the bonding position)].
the effect of invention
Aspect of the present invention provides the magenta toner with spectral reflection characteristics such as high-color rendering and the transparency and high-light-fastness.
The accompanying drawing explanation
The dye composition that Fig. 1 is the aspect according to the present invention (5) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
The dye composition that Fig. 2 is the aspect according to the present invention (6) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
The dye composition that Fig. 3 is the aspect according to the present invention (7) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
The dye composition that Fig. 4 is the aspect according to the present invention (8) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
The dye composition that Fig. 5 is the aspect according to the present invention (10) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
The dye composition that Fig. 6 is the aspect according to the present invention (24) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
The dye composition that Fig. 7 is the aspect according to the present invention (25) is at DMSO-d 6in under 80 ℃, 400MHz 1h-NMR spectrum.
Embodiment
Describe each aspect of the present invention in detail below by embodiment.For solving the problem of above-mentioned prior art, the inventor has conducted in-depth research and has found to use the water-insoluble dye composition meaned by formula (1) that the magenta toner with excellent colour rendering and the transparency and high-light-fastness is provided with colorant as magenta toner.This discovery has caused of the present invention completing.
Formula 1
Figure BDA0000383456350000041
[in its Chinese style (1), R 1, R 5, R 6and R 10mean independently of one another alkyl; R 3and R 8mean independently of one another hydrogen atom, alkyl, alkoxy or aryloxy group; And R 2, R 4, R 7and R 9mean independently of one another hydrogen atom or the acylamino-meaned by formula (2), condition is R 2, R 4, R 7and R 9one of at least mean the acylamino-meaned by formula (2):
Formula 2
Figure BDA0000383456350000042
(in its Chinese style (2), R 11mean alkyl, naphthenic base, aryl, aralkyl, thiazolinyl or heterocyclic radical; And * means the bonding position)].
The water-insoluble dye composition meaned by formula (1) below will be described.
The water-insoluble dye composition meaned by formula (1) has the high-affinity to organic solvent.The term " water-insoluble " that attention is used in aspect the present invention means that the dissolubility in water is less than 1 quality %.
In formula (1), by R 1, R 5, R 6and R 10the example of the alkyl meaned comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl and the tert-butyl group.
In formula (1), each free R 1, R 5, R 6and R 10the alkyl meaned can be substituted base and replace.Spendable substituent example comprises alkoxy, cyano group and halogen atom.There is substituent R 1, R 5, R 6and R 10instantiation comprise hydroxyethyl, methoxy ethyl, cyanoethyl and trifluoromethyl.
In formula (1), R 1, R 5, R 6and R 10can desirably be selected from above listed functional group.At R 1and R 6while meaning identical functional group and at R 5and R 10mean can easily produce water-insoluble dye composition in the situation of identical functional group.In addition, mean in functional group that separately in the situation of methyl, raw material is easy to available.
In formula (1), by R 3and R 8the example of the alkyl meaned comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl and the tert-butyl group.
In formula (1), by R 3and R 8the example of the alkoxy meaned comprises methoxyl, ethoxy and isopropoxy.
In formula (1), by R 3and R 8the example of the aryloxy group meaned comprises phenoxy group and naphthoxy.
In formula (1), by R 3and R 8alkyl, alkoxy and the aryloxy group meaned can be substituted base and replace.Spendable substituent example comprises alkyl, aryl, aralkyl, hydroxyl, carbamyl, sulfamoyl, alkoxy and cyano group and halogen atom.There is substituent R 3and R 8instantiation comprise hydroxyethyl, methoxy ethyl, cyanoethyl, trifluoromethyl, methoxy ethoxy, hydroxy ethoxy, to methoxyphenoxy, O-methoxy phenoxy group, toloxyl and xylyloxy.
In formula (1), R 3and R 8each can desirably be selected from above listed functional group and hydrogen atom.At R 3and R 8meaning separately can provide gratifying photostability in the situation of methyl, ethyl or propyl group.At R 3and R 8mean separately to consider the easiness R of production in the situation of the group except hydrogen atom 3and R 8can mean identical functional group.
In formula (1), R 2, R 4, R 7and R 9mean independently of one another hydrogen atom or the acylamino-meaned by formula (2).R 2, R 4, R 7and R 9one of at least mean the acylamino-meaned by formula (2).For the water-insoluble dye composition with high-color rendering and high-light-fastness, R are provided 2, R 4, R 7and R 9one of at least need to mean the acylamino-meaned by formula (2).
Especially, from strengthening colour rendering and sunproof viewpoint, R in formula (1) 2, R 4, R 7and R 9each of 2 to 4 can mean the acylamino-meaned by formula (2).In this case, consider the easiness of production, acylamino-can be mutually the same.In addition, R in formula (1) 2to R 7can mean identical functional group, and R in formula (1) 4and R 9can mean identical functional group.
In formula (2), by R 11the example of the alkyl meaned comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl and the tert-butyl group.
In formula (2), by R 11the example of the naphthenic base meaned comprises cyclopentyl, cyclohexyl and suberyl.
In formula (2), by R 11the example of the aryl meaned is phenyl.
In formula (2), by R 11the example of the aralkyl meaned comprises benzyl and 2-phenethyl.
In formula (2), by R 11the example of the thiazolinyl meaned comprises vinyl, 1-propenyl, 2-propenyl, 1-methyl ethylene, 1-butenyl group, 2-butenyl group and 3-butenyl group.
In formula (2), by R 11the example of the heterocyclic radical meaned comprises imidazole radicals, benzimidazolyl, pyrazolyl, benzopyrazoles base, triazolyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazole Ji, oxazolyl, benzoxazolyl, thiadiazolyl group, pyrrole radicals, benzopyrrole base, indyl, isoxazolyl, benzoisoxazole base, thienyl, benzothienyl, furyl, benzofuranyl, pyridine radicals, quinolyl, isoquinolyl, pyridazinyl, pyrimidine radicals, pyrazinyl, cinnolines base, 2,3-phthalazinyl, quinazolinyl, quinoxalinyl and triazinyl.
In formula (2) by R 11the functional group meaned can be substituted base and replace.Spendable substituent example comprises alkyl, aryl, aralkyl, thiazolinyl, alkoxy, cyano group, alkylamino, sulfoalkyl, carbamyl, sulfamoyl and sulfonamido (sulfonylamino groups) and halogen atom.There is substituent R 11instantiation comprise hydroxyethyl, methoxy ethyl, cyanoethyl, trifluoromethyl, p-methylphenyl, p-methoxyphenyl and Chloro-O-Phenyl.
In formula (2), R 11can desirably be selected from above listed functional group.Consider colour rendering, R 11can mean alkyl, naphthenic base, aryl or aralkyl.Consider the easiness of production, R 11can mean alkyl or aryl.Consider photostability preferably, R 11can mean straight chained alkyl.
Shown in following scheme, for the water-insoluble dye composition meaned by formula (1), there is the dynamic isomer for example meaned by formula (3) and (4).These dynamic isomers also within the scope of the invention.
In formula (3) and (4), R 1to R 10definition and the R in formula (1) 1to R 10identical.
The water-insoluble dye composition meaned by formula (1) can synthesize according to known production method.Below exemplary synthetic schemes will be shown.
In above-claimed cpd B, C and D, R 1to R 10definition and the R in formula (1) 1to R 10identical.
In the scheme of above example, the water-insoluble dye composition meaned by formula (1) synthesizes by the second condensation step shown in the first condensation step shown in the first row and the second row.
In the first condensation step, organic solvent and condensation agent exist or not in the presence of heating condensation compound A and compd B with synthetic compound C.Shown in the second row, heating condensation in the first condensation step synthetic Compound C and Compound D to provide the water-insoluble dye composition meaned by formula (1).
As compd B and the C of anil and compd A easily is obtained commercially and can be easily synthetic by known method.
Below will be described in the above synthetic schemes illustrated the organic solvent for condensation reaction.In described step, spendable organic solvent is not particularly limited as long as organic solvent does not participate in reaction.The example comprises methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, toluene, dimethylbenzene, ethylene glycol, 1-METHYLPYRROLIDONE, N, N-dimethyl acetamide, DMF, dimethyl sulfoxide, sulfolane, chlorobenzene, dichloro-benzenes, trichloro-benzenes and nitrobenzene.According to the dissolubility of matrix, these compounds can be used alone or in combination of two or more.
The example that is used for the condensation agent of described step comprises magnesium oxide, zinc chloride and aluminum chloride.
Described step is usually carried out and was usually completed in 24 hours in the temperature range of 60 ℃ to 220 ℃.
Temperature of reaction in the first condensation step is preferably at 60 ℃ to 100 ℃ and more preferably in the scope of 70 ℃ to 90 ℃.In this scope, reaction rate is suitable, and suppresses overreaction, is convenient to thus purifying.Temperature of reaction in the second condensation step is preferably at 120 ℃ to 220 ℃ and more preferably in the scope below 180 ℃.In this scope, reaction rate is suitable, and suppresses satisfactorily the decomposition of the compound of formation.
At synthetic wherein R in formula (1) 1to R 5mean identical functional group and R wherein 6to R 10mean that in the situation of water-insoluble dye composition of identical functional group, in scheme, compd B and D can be identical compounds.Therefore, in this case, the water-insoluble dye composition meaned by formula (1) can synthesize by the single condensation step by compd A.Described reaction is usually carried out and was usually completed in 24 hours under 100 ℃ to 220 ℃.
By above-mentioned reaction scheme, synthetic end-product is processed according to the common aftertreatment for organic synthesis, then carries out such as recrystallization, the purifying of precipitation or column chromatography etc. again, to provide the high-purity dye composition.The water-insoluble dye composition meaned by formula (1) can pass through, for example 1h-nuclear magnetic resoance spectrum, LC/TOF MS and UV/Vis spectrophotometric method are identified.
The water-insoluble dye composition meaned by formula (1) can be used alone as colorant.As required, the two or more water-insoluble dye compositions that meaned by formula (1) can be used in two or more combinations.Alternatively, the water-insoluble dye composition meaned by formula (1) can be used with known magenta pigment or dye combinations.In addition, the water-insoluble dye composition meaned by formula (1) can be used as mordant pigment.
Below the magenta toner of the aspect according to the present invention will be described.
The water-insoluble dye composition that the magenta toner of aspect comprises resin glue and meaned by formula (1) according to the present invention, and can comprise wax and charge control agent etc. as required.
The example of resin glue comprises the multipolymer of following monomer: the polymerizable vinyl monomer, styrenic monomers for example, as styrene, α-methyl styrene, α-ethyl styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, adjacent ethyl styrene, an ethyl styrene with to ethyl styrene; The methacrylic acid derivative monomer, for example methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid dodecane ester, methacrylic acid stearyl, methacrylic acid Shan Yu ester, 2-Ethylhexyl Methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylonitrile, Methacrylamide, N-methyl acrylamide, N, N-dimethylmethacryl amide and N-(3-dimethyl aminopropyl) Methacrylamide; The acrylic acid derivative monomer, for example methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, acrylic acid dodecane ester, stearyl acrylate base ester, acrylic acid Shan Yu ester, 2-EHA, dimethylaminoethyl acrylate, acrylic acid lignocaine ethyl ester, vinyl cyanide, acrylamide, N methacrylamide, N, N-DMAA, N-ethyl acrylamide, N-(methylol) acrylamide and N-(hydroxyethyl) acrylamide, and olefinic monomer, for example butadiene, isoprene and cyclohexene; By combining the multipolymer of its two or more preparations; Potpourri with homopolymer and multipolymer.Its further example comprises epoxy resin, vibrin, urethane resin, polyamide, celluosic resin, polyether resin and non-vinyl condensation resin; The potpourri of these resins and above-mentioned vinylite; With the graft polymer by preparing with polymerization of vinyl monomer under existing at these.
Resin glue can be used alone.Alternatively, usually, can suitably monomer be mixed with each other and with theoretical glass transition temperature (Tg) (J.Brandrup and E.H.Immergut, Eds.; " Polymer Handbook ", Third edition; John Wiley& Sons, U.S.A., 1989; Pp209-277) in the scope of 40 ℃ to 75 ℃, such mode is used.In situation at theoretical glass transition temperature in above-mentioned scope, keep the image transparency to keep satisfactorily bin stability and the stability when printing a large amount of paper simultaneously.
The instantiation of wax comprises pertroleum wax, for example paraffin, microcrystalline wax and vaseline with and derivant; Montan wax and derivant thereof; Synthetic chloroflo and the derivant thereof by fischer tropsch process; Polyolefin-wax, for example Tissuemat E and derivant thereof; And natural wax, for example Brazil wax and candelila wax and derivant thereof.Described derivant comprises their oxide, segmented copolymer and the graft modification product of they and vinyl monomer.The further example of wax comprises alcohol, for example higher fatty alcohol; Fatty acid, for example stearic acid and palmitic acid; Fatty acid amide; Fatty acid ester; Castor oil and derivant thereof; Vegetable wax; And animal wax.These waxes can be used alone or as required with two or more being used in combination.
Wax preferably has 50 ℃ to 200 ℃ and the more preferably fusing point of 50 ℃ to 150 ℃.The peak temperature of main endothermic peak in the curve that the term used in aspect the present invention " fusing point " means to measure by differential scanning calorimetry (DSC) according to ASTM D3418-82.Particularly, being determined as follows of the fusing point of wax: measured in the measurement temperature range of 30 ℃ to 200 ℃ with the rate of heat addition of 5 ℃/min with differential scanning calorimeter (DSC822 is manufactured by Mettler Toledo International Inc.).Carry out for the second time temperature-rise period to obtain the DSC curve in the temperature range of 30 ℃ to 200 ℃ under normal temperature and normal wet condition.The peak temperature of main endothermic peak in the DSC curve is defined as to fusing point.
Wax content with respect to 100 mass parts resin glues preferably in 1 to 25 mass parts and more preferably in the scope of 3 to 20 mass parts.
Although use the dye composition meaned by formula (1) as the colorant in the basic toner-particle in the magenta toner that is contained in the aspect according to the present invention, yet as required, can by other colorant and its combination.
The example of other colorant capable of being combined comprises azo-compound, azo-metal complex, pyrrolo-pyrrole-dione compound, anthraquinone compounds, quinacridone compound, basic-dyeable fibre color lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, perylene compound, methylidyne compound and the allyl amide compound (allylamide compound) of condensation.Its instantiation includes, but are not limited to C.I. pigment orange 1,5,13,15,16,34,36,38,62,64,67,72 and 74, C.I. paratonere 2, 3, 4, 5, 6, 7, 12, 16, 17, 23, 31, 32, 41, 48, 48:1, 48:2, 48:3, 48:4, 53:1, 57:1, 81:1, 112, 122, 123, 130, 144, 146, 149, 150, 166, 168, 169, 170, 176, 177, 178, 179, 181, 184, 185, 187, 190, 194, 202, 206, 208, 209, 210, 220, 221, 224, 238, 242, 245, 253, 254, 255, 258, 266, 269 and 282, C.I. pigment violet 13,19,25,32 and 50, with the various colorants that are categorized as its derivant.
The total content of colorant can be in the scope of 1 to 20 mass parts with respect to 100 mass parts resin glues.
As required, according to the present invention, the magenta toner of aspect can comprise charge control agent.This makes its optimally control response in the friction belt electric weight of toning system.
Can use the charge control agent of any known charge control agent as the basic toner-particle of the magenta toner for aspect according to the present invention.Especially, consider that rapid development and picture steadiness can be used frictional electrification speed fast and can stably keep the charge control agent of certain friction belt electric weight.In by the direct polymerization method, producing the situation of toner, can use the degree that suppresses polymerization low and basically do not comprise the charge control agent that dissolves in the component in the water-based dispersion medium.
But the example that allows the charge control agent of toner negative charging comprises polymkeric substance and the multipolymer of each self-contained sulfonic group, sulphonate-base or sulfonate group; Salicyclic acid derivatives and metal complex thereof; The Monoazo metal compound; The metal acetylacetonates compound; Aromatic hydroxycarboxylic acids (aromatic oxycarboxylic acid); Aromatics list and polycarboxylic acid and slaine thereof, its acid anhydrides and its ester; Phenol derivatives, for example bis-phenol; Urea derivative; Metallic naphthoic acid compound; Boron compound; Quaternary ammonium salt; Calixarenes; With the resene charge control agent.
Allow the example of the charge control agent that toner can be just charged to comprise nigrosine and with the nigrosine of the slaine modification of for example fatty acid; Guanidine compound; Imidazolium compounds; Salt, quaternary ammonium salt for example, as 1-hydroxyl-4-naphthalene sulfonic acids tributyl benzyl ammonium and tetrafluoro boric acid tetrabutylammonium, and its microcosmic salt analog and mordant pigment thereof; Kiton colors and mordant pigment thereof (example of color lake agent comprises phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, the ferricyanide and ferrocyanide); The slaine of higher fatty acid; Two organotin oxides, for example Dibutyltin oxide, dioctyl tin oxide and dicyclohexyl tin oxide; Two organotin borates, for example boric acid dibutyl tin, boric acid dioctyl tin and boric acid dicyclohexyl tin; With the resene charge control agent.
In these charge control agents, two or more reagent capable of being combined.
According to the present invention, the toner of aspect can be magnetic color tuner or nonmagnetic toner.In the situation of toner as magnetic color tuner aspect using according to the present invention, can introduce known magnetic material.
In magenta toner aspect according to the present invention, can be by external additive, the surface that for example inorganic fine powder and resin thin particle add the basic toner-particle that comprises resin glue and colorant to.The example of inorganic fine powder comprises the fine powder be comprised of silicon dioxide, titanium dioxide, aluminium oxide and double oxide thereof, and by making these fine powders carry out the powder of surface treatment production.The fine grain example of resin comprises the fine grained be comprised of vinylite, vibrin and silicone resin.They work the function that strengthens mobility.
Example for the production of the method for the magenta toner of the aspect according to the present invention comprises suspension polymerization, emulsification aggregation method, suspension comminution granulation, emulsion polymerization and polishing, and these are known methods.In these production methods, from realize the viewpoint of low environmental load and good granularity controllability at production period, can adopt especially such as suspension polymerization, emulsification aggregation method and suspension comminution granulation etc. to carry out the production method of granulation in aqueous medium.
The method of producing toner below will be described.
At first, below will describe by suspension polymerization and produce toner.
In passing through the situation of suspension polymerization product in next life red color tone toner, from improving the viewpoint of the dispersiveness of colorant toner, can be produced the dispersion steps that the colorant that wherein will comprise the dye composition meaned by formula (1) is dispersed or dissolved in the so-called masterbatch of medium in advance.
For example, be prepared as follows masterbatch: will comprise the colorant of the water-insoluble dye composition meaned by formula (1) and the dispersion medium that for example resin as required under agitation little by little adds the toner that will be scattered here and there to, and make thus component fully mix with dispersion medium.Then applying mechanical shear stress with dispersion machine to potpourri stably dissolves colorant or fine disperses.
The dispersion medium that can be used for masterbatch is not particularly limited.For dissolubility and the dispersiveness that colorant is provided effectively, dispersion medium can be water-insoluble solvent.The instantiation of water-insoluble solvent comprises ester, for example methyl acetate, ethyl acetate and propyl acetate; Aliphatic hydrocrbon, for example hexane, octane, sherwood oil and cyclohexane; Aromatic hydrocarbon, for example benzene, toluene and dimethylbenzene; With halogen-containing hydrocarbon, for example phenixin, triclene and tetrabromoethane.
Dispersion medium for masterbatch can also be polymerisable monomer.But but but polymerisable monomer for addition polymerization monomer or condensation polymerization monomer and can be the addition polymerization monomer.Its instantiation comprises styrenic monomers, for example styrene, α-methyl styrene, α-ethyl styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, adjacent ethyl styrene, an ethyl styrene and to ethyl styrene; The methacrylic acid derivative monomer, for example methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid dodecane ester, methacrylic acid stearyl, methacrylic acid Shan Yu ester, 2-Ethylhexyl Methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylonitrile, Methacrylamide, N-methyl acrylamide, N, N-dimethylmethacryl amide and N-(3-dimethylamino-propyl) Methacrylamide; The acrylic acid derivative monomer, for example methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, acrylic acid dodecane ester, stearyl acrylate base ester, acrylic acid Shan Yu ester, 2-EHA, dimethylaminoethyl acrylate, acrylic acid lignocaine ethyl ester, vinyl cyanide, acrylamide, N methacrylamide, N,N-DMAA, N-ethyl acrylamide, N-(methylol) acrylamide and N-(hydroxyethyl) acrylamide; And olefinic monomer, for example butadiene, isoprene and cyclohexene.
As required, also can add resin to masterbatch.As the resin that adds masterbatch to, can use the resin that can be used as resin glue.Its instantiation comprises polystyrene resin, styrol copolymer, polyacrylic resin, polymethacrylate resin, polyacrylate resin, polymethacrylate resin, acrylate copolymer, methacrylic acid copolymer, polyvinyl ether resin, polyvinyl methyl ether resin, polyvinyl alcohol resin and polyvinyl butyral resin.These resins can be separately or as required with two or more being used in combination.
As required, masterbatch can further comprise auxiliary agent.Its instantiation comprises surfactant, pigment dispersing agent and non-pigment dispersing agent, filler, standard agent (standardizer), defoamer, antistatic agent, dust-proofing agent, extender, deep or light colorant (shading colorant), antiseptic, drying retarder, rheology control adjuvant, wetting agent, antioxidant, ultraviolet light absorber, light stabilizer and their combination.
After the masterbatch preparation, remaining polymerisable monomer and wax etc. are added to wherein with the preparation polymerizable monomer composition.Can be by polar resin, for example vibrin or polycarbonate resin add polymerizable monomer composition to.According to the balanced polarities between polymerizable monomer composition and aqueous dispersion medium, the polar resin of interpolation forms film or exists with concentration gradient to center from the surface of each basic toner-particle on the surface of toner-particle.In addition, make and can regulate the state that is present in the colorant in toner with the use of the interactional polar resin of colorant of the aspect according to the present invention.
In the magenta toner prepared by suspension polymerization, crosslinking chemical can be used in order to increase the physical strength of toner and the molecular weight of adjusting resin glue in the synthetic binder resin.
The example of crosslinking chemical comprises, but is not confined to especially bifunctional cross-linker, for example divinylbenzene, two (4-acryloxy polyethoxy phenyl) propane, glycol diacrylate, the 1,3-BDO diacrylate, the BDO diacrylate, the 1,5-PD diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyglycol #200, the diacrylate of #400 and #600, propylene glycol diacrylate, polypropyleneglycol diacrylate, polyester acrylate, ethylene glycol dimethacrylate, the 1,3-BDO dimethylacrylate, the BDO dimethylacrylate, the 1,5-PD dimethylacrylate, HDDMA, neopentylglycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyglycol #200, the dimethylacrylate of #400 and #600, the dipropylene glycol dimethylacrylate, polypropylene glycol dimethacrylate and polyester dimethylacrylate.
The example of multifunctional crosslinking chemical comprises, but be not confined to especially, pentaerythritol triacrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, the oligoester acrylate, pentaerythritol acrylate trimethyl, the trimethylolethane trimethacrylate methacrylate, trimethylol-propane trimethacrylate, pentaerythritol tetramethylacrylate, the oligoester methacrylate, 2, two (the 4-methacryloxy phenyl) propane of 2-, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and trimellitic acid triallyl.
Consider fixation performance and the resistant damage property of toner, these crosslinking chemicals preferably be take separately with respect to 100 mass parts polymerisable monomer as 0.05 to 10 mass parts the more preferably amount use of 0.1 to 5 mass parts.
The example that can be used for the dispersion machine of the method comprises, but is not confined to especially, rotational shear type homogenizer, and such as the medium-type dispersion machine of bowl mill, sand mill and masher etc., and high pressure subtend collision type dispersion machine.
In aqueous medium, disperse polymerizable monomer composition granulation to form the drop of polymerizable monomer composition.The suspending liquid that uses polymerization initiator, in aqueous medium, the polymerisable monomer polymerization in drop is comprised to toner-particle with preparation.Then toner-particle is separated from the suspending liquid that comprises toner-particle.Washing the dry toner-particle separated.
The example of polymerization initiator comprises known polymerization initiator.Its instantiation comprises azo-compound, organic peroxide, inorganic peroxide, organometallics and Photoepolymerizationinitiater initiater.Its more specifically example comprise azo-compound, for example 2,2'-azo two (isobutyronotrile), 2,2'-azo two (2-methylbutyronitrile), 2,2'-azo two (4-methoxyl-2,4-methyl pentane nitrile), 2,2'-azo two (2, the 4-methyl pentane nitrile) and dimethyl 2,2'-azo two (isobutyrate); Organic peroxide polymerization initiator, for example benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide isopropyl monocarbonate, tertiary hexyl peroxide benzoate and tert butyl peroxy benzoate; Inorganic peroxide polymerization initiator, for example potassium persulfate and ammonium persulfate; And redox initiator, for example hydrogen peroxide-ferrous system, BPO-dimethyl benzene amine system and cerium (IV) salt-ol system.The example of Photoepolymerizationinitiater initiater comprises acetophenone, benzoin ether and ketal.
Consider the degree of polymerization, the use amount of polymerization initiator with respect to 100 mass parts polymerisable monomers preferably in 0.1 to 20 mass parts and more preferably in the scope of 0.1 to 10 mass parts.The type of polymerization initiator is omited microvariations according to polymerization.With reference to its 10 hours half life temperatures, these polymerization initiators can be used with two or more combinations separately or as required.
From the viewpoint of the gratifying stability that realizes polymerizable monomer composition, for the aqueous medium of suspension polymerization, can comprise dispersion stabilizer.The example of spendable dispersion stabilizer comprises known inorganic and organic dispersion stabilizer.
In above-mentioned dispersion stabilizer, aspect the present invention in, consider in washing step subsequently and remove dispersion stabilizer, can use the difficult water-soluble inorganic dispersion stabilizer dissolved in acid.In aspect of the present invention, in the difficult water-soluble inorganic dispersion stabilizer of use prepares the situation of aqueous dispersion medium, consider the stability of drop aqueous medium from polymerizable monomer composition, the use amount of dispersion stabilizer can be 0.2 to 2.0 mass parts with respect to 100 mass parts polymerisable monomers.Consider the stability of drop, the water that can to use with respect to 100 mass parts polymerizable monomer composition be 300 to 3000 mass parts prepares aqueous medium.
In suspension polymerization, disperse polymerizable monomer composition and the method for the drop granulation of polymerizable monomer composition is not particularly limited in aqueous medium.For example, can adopt the known method that uses rotational shear homogenizer, high pressure subtend collision type dispersion machine or ultrasonic dispersing machine etc.
Washing process in washing step is not particularly limited, yet comprises by filtering, with distilled water, under agitation washing the gained solid, and filtering mixt and make the suspending liquid that comprises toner-particle carry out Separation of Solid and Liquid.From realizing the viewpoint of gratifying toner charging property, but repeated washing until the conductivity of filtrate reach below 150 μ S/cm.
In drying steps, can use known method usually, for example oscillating mode fluidized drying method, spray drying process, freeze-drying and quick gunite (flash jet method).Consider charging property, dried basic toner-particle preferably has the following and more preferably liquid water content of 1.0 quality % of 1.5 quality %.
Next, will describe by the emulsification aggregation method and produce toner.
At first, preparation comprises the particulate resin dispersion that is scattered in the resin particle in aqueous medium, and the coloring agent particle dispersion liquid that is included in the coloring agent particle that in aqueous medium, dispersion contains the water-insoluble dye composition meaned by formula (1).In addition, as required, the Wax particles dispersion liquid that preparation comprises the Wax particles be scattered in aqueous medium.The gained dispersion liquid is mixed to prepare potpourri (dispersion steps).Then the particle aggregation comprised in the potpourri that makes to prepare in above-mentioned steps is aggregated particle (agglomeration step).The heating aggregated particle is with coalescent (agglomeration step).Filtering, wash also dry agglomerate particles is toner.
The term used in dispersion steps " aqueous medium " refers to main moisture medium.The instantiation of aqueous medium comprises water, moisture and the medium of pH adjusting agent and the medium of moisture and organic solvent.
The resin that forms the resin particle in particulate resin dispersion is not particularly limited, as long as described resin is what to be applicable to for binder resin for toner.
By known method, prepared by particulate resin dispersion.For example, comprising by vinyl monomer, in the situation of the particulate resin dispersion of the resin particle that particularly styrene monomer is made, can prepare by the emulsion polymerization of monomer under existing at surfactant by particulate resin dispersion.
For example, in the situation of the resin prepared in the method by other (, vibrin), by resin dissolves in the lipophilicity solvent that there is relatively low solubleness in water to prepare resin solution.The gained resin solution is added together with polyelectrolyte to aqueous medium with ionic surfactant.Use dispersion machine, for example homogenizer forms the fine droplets of resin solution.Evaporating solvent and particulate resin dispersion is provided under heating or decompression.Alternatively, can be by such as comprising adding surfactant to resin and using such as dispersion machines such as homogenizers, making gained potpourri emulsification method of disperseing in water, or phase conversion emulsifying prepares particulate resin dispersion.
Consider the granulation of aggregation and the toner-particle of particle, the resin particle in particulate resin dispersion preferably has 0.005 to 1.0 μ m the more preferably median particle diameter of the volume reference of 0.01 to 0.4 μ m.
The particle mean size of resin particle can be measured by for example dynamic light scattering (DLS) method, laser scattering method, centrifugal settling method, FFF (field-flow fractionation method) or electric explorer method.The term used in aspect of the present invention " particle mean size " refers to 50% accumulation granularity (D50) of the volume reference measured under 20 ℃ and the solid composition of 0.01 quality % by (DLS) method of the dynamic light scattering as described below or laser Doppler method, unless otherwise mentioned.
In addition, the particulate resin dispersion that comprises colorant can be by be supplied to resin glue in aqueous medium and disperse resin glue and colorant to prepare in aqueous medium simultaneously together with colorant.
The coloring agent particle dispersion liquid can comprise surfactant in order to make the decentralized stabilization of coloring agent particle.The example of surfactant comprises water soluble polymer, mineral compound and ion or non-ionics.Consider that its surfactivity can be used ionic surfactant, particularly anionic surface active agent.
Consider its washability in downstream procedures, surfactant preferably has below 10,000 and the more preferably molecular weight below 5,000.Simultaneously, consider its surfactivity, surfactant preferably has more than 100 and the more preferably molecular weight more than 200.
The instantiation of surfactant comprises water soluble polymer, for example polyvinyl alcohol (PVA), methylcellulose, carboxymethyl cellulose and sodium polyacrylate; Anionic surface active agent, for example neopelex, sodium stearyl sulfate, sodium oleate, sodium laurate and potassium stearate; Cationic surfactant, for example lauryl amine acetate and lauryl trimethyl ammonium chloride; Amphoteric surfactant, for example lauryl dimethyl amine oxide; Non-ionics, for example polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl amine; And mineral compound, for example tricalcium phosphate, aluminium hydroxide, calcium sulphate, calcium carbonate and barium carbonate.These compounds can be separately or as required with two or more being used in combination.
Consider the washability in downstream procedures, the use amount of surfactant with respect to 100 mass parts colorants in 0.01 to 10 mass parts, preferred 0.1 to 5.0 mass parts, and more preferably in the scope of 0.5 to 3.0 mass parts.
By known method, prepared by the coloring agent particle dispersion liquid.For example, can use the rotational shear homogenizer, such as the medium-type dispersion machine of bowl mill, sand mill and masher etc., or high pressure subtend collision type dispersion machine etc.
By known method, prepared by the wax dispersion for dispersion steps.
Particulate resin dispersion, coloring agent particle dispersion liquid and wax dispersion can further comprise other toner component as required.
The method that forms aggregated particle in agglomeration step is not particularly limited.Can adopt and comprise and add the method that pH adjusting agent, flocculating agent and stabilizing agent are waited until said mixture and suitably apply machine power (for example stirring) to the gained potpourri under heating.
The example of pH adjusting agent comprises, but is not confined to especially alkali, for example ammonia and NaOH; And acid, for example nitric acid and citric acid.
The example of flocculating agent comprises the surfactant had separately with the opposite polarity polarity of surfactant for discrete particles; Inorganic metal salt, for example sodium chloride, magnesium carbonate, magnesium chloride, magnesium nitrate, magnesium sulphate, lime chloride and aluminium sulphate; With divalence or high-valency metal complex more.
The example of stabilizing agent comprises surfactant; With the aqueous medium that comprises surfactant.
The example of surfactant comprises, but is not confined to especially water soluble polymer, for example polyvinyl alcohol (PVA), methylcellulose, carboxymethyl cellulose and sodium polyacrylate; Anionic surface active agent, for example neopelex, sodium stearyl sulfate, sodium oleate, sodium laurate and potassium stearate; Cationic surfactant, for example laurylamine acetate and lauryl trimethyl ammonium chloride; Amphoteric surfactant, for example lauryl dimethyl amine oxide; Non-ionics, for example polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl amine; And mineral compound, for example tricalcium phosphate, aluminium hydroxide, calcium sulphate, calcium carbonate and barium carbonate.These compounds can be separately or as required with two or more being used in combination.
The particle mean size of the aggregated particle herein formed usually can be suitable with the particle mean size of the toner that will produce.Coalescent for preventing aggregated particle, can suitably add pH adjusting agent and surfactant etc.
In agglomeration step, the heating aggregated particle makes particles coalesce, forms thus toner-particle.Heating-up temperature can be the glass transition temperature (Tg) that is contained in the resin in aggregated particle and the temperature between the resin decomposition temperature.For example, under the stirring in being similar to agglomeration step, by adding surfactant or regulating pH, stop the carrying out assembled.The heating aggregated particle, to the glass transition temperature that is equal to or higher than the resin in resin particle, makes aggregated particle coalescent thus.Can be to make the abundant coalescent time of particle heat time heating time.Particularly, heat time heating time can be in the scope of approximately 10 minutes to approximately 10 hours.
In addition, before or after agglomeration step, can add said mixture to by comprising dispersion fine grain fine grained dispersion liquid wherein, thereby the surface that thus fine grained is attached to aggregated particle forms the toner-particle have separately nucleocapsid structure.
The suspending liquid that comprises toner-particle that makes to obtain after agglomeration step filters under suitable condition, washs and is dry etc., and toner is provided thus.In this case, can fully wash toner-particle in order to there is the sufficient charged characteristic of toner.
Washing step and drying steps are identical with those in the situation of producing toner by suspension polymerization.
Next, will describe by the suspension comminution granulation and produce toner.
Production method by the suspension comminution granulation does not comprise the high-temperature heating step.Described method causes the resin that occurs when using low melt wax and the inhibition of the compatibilized between the wax component.This glass transition temperature that prevents toner is because compatibilized reduces.In addition, for the toner materials that forms resin glue, the suspension comminution granulation provides the selection of extensive options.Therefore be easy to use to there is the vibrin of favourable fixation performance as key component.Therefore, the suspension comminution granulation is advantageously used in and produces the toner with resin composition of not producing by suspension polymerization.
To comprise the colorant, resin glue of the water-insoluble dye composition meaned by formula (1) and optional wax component etc. is mixed in solvent with the solvent-laden composition of preparation bag.The solvent-laden composition of bag is scattered in aqueous medium so that wrap the grain granulation of solvent-laden composition, the suspending liquid of the solvent-laden composition of bag is provided thus.Under reduced pressure from the suspending liquid that wraps solvent-laden composition, except desolventizing, provide the suspending liquid that comprises toner-particle.Separate toner-particle the suspending liquid that comprises basic toner-particle from gained.Washing the dry toner-particle separated.
Wrapping solvent-laden composition can prepare by making to comprise the dispersion liquid and the second solvent that are scattered in the colorant in the first solvent.; make the colorant that comprises the water-insoluble dye composition meaned by formula (1) be scattered in fully the first solvent; then mix with other toner materials together with the second solvent, thereby each toner component that is contained in toner is existed with gratifying disperse state in toner-particle.
The example that can be used for wrapping the solvent of solvent-laden composition comprises aromatic hydrocarbons, for example toluene and dimethylbenzene; Aliphatic hydrocarbon, for example hexane, heptane and octane; Halogen-containing hydro carbons is methylene chloride, chloroform, ethylene dichloride, α-trichloroethanes and phenixin for example; Alcohols is methyl alcohol, ethanol, butanols and isopropyl alcohol for example; Polyalcohols is ethylene glycol, propylene glycol, diglycol and triethylene glycol for example; The cellosolve class is methyl cellosolve and ethyl cellosolve for example; Ketone is acetone, methyl ethyl ketone and methyl isobutyl ketone for example; Ethers is phenmethylol ether, phenmethylol isopropyl ether and tetrahydrofuran for example; With ester class for example methyl acetate, ethyl acetate and butyl acetate.These solvents can be separately or as required with two or more being used in combination.In these solvents, can use the solvent that there is low boiling and can fully dissolve resin glue to be convenient to remove the solvent in toner-particle suspending liquid.
Consider the dissolubility of resin glue and except the easiness of desolventizing, for the amount of the solvent that wraps solvent-laden composition with respect to 100 mass parts resin glues preferably in 50 to 5000 mass parts and more preferably in the scope of 120 to 1000 mass parts.
Can use aqueous medium for suspension polymerization as the aqueous medium for the comminution granulation that suspends.
But aqueous medium can comprise the miscible solvent of water.The example of the solvent that can comprise comprises methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, dimethyl formamide, tetrahydrofuran, methyl cellosolve, acetone and methyl ethyl ketone.These solvents can be separately or as required with two or more being used in combination.
In the suspension comminution granulation, in aqueous medium, disperse the particle of the solvent-laden composition of bag the solvent-laden composition of granulation bag to be not particularly limited with the method that the suspending liquid that wraps solvent-laden composition is provided.For example, can adopt the known method that uses rotational shear homogenizer, high pressure subtend collision type dispersion machine or ultrasonic dispersing machine etc.
From the suspending liquid that wraps solvent-laden composition, except the example of desolventizing with method that the suspending liquid that comprises toner-particle is provided, comprise, the temperature by the whole system that raises gradually is with solvent flashing, by the method that makes dry gas flow or evaporate and remove the solvent in suspending liquid by the pressure reduced in whole system in system.Alternatively, suspending liquid is spurted into to dry atmosphere to evaporate and to remove the aqueous medium together with solvent in the solvent-laden composition of bag.
The suspending liquid that makes gained comprise toner-particle filters under suitable condition, washs and is dry etc., and toner is provided thus.In this case, can fully wash toner-particle in order to there is the sufficient charged characteristic of toner.
Washing step and drying steps are identical with those in the situation of producing toner by suspension polymerization.
Next, will describe by polishing and produce toner.
In by polishing, producing the situation of toner, toner can be with known production equipment, and for example known mixer, heat kneading machine and the grader of those skilled in the art produced.
Use mixer, for example Henschel mixer or bowl mill fully mix described material together.Use heat kneading machine, for example then roller, kneader (kneader) or extruder molten mixture are also mediated so that resin compatible.Wax and magnetic material are scattered in wherein.Cooling and the sclerosis after, grinds with classification so that toner to be provided.
Example for the resin glue of the toner by comminuting method production comprises vinylite, vibrin, epoxy resin, urethane resin, polyvinyl butyral resin, terpene resin, phenolics, aliphatic series and alicyclic hydrocarbon resin, aromatic petroleum resin, rosin, modified rosin.In these resins, consider that charging property and fixation performance can be used vinylite and vibrin.Especially, use vibrin effectively to improve charging property and fixation performance.
These resins can be used alone or in combination of two or more.
In as potpourri, using the situation of two or more resins, can mix the resin with different molecular weight in order to control the viscoelastic property of toner.
Each resin glue preferably has 45 ℃ to 80 ℃ and the more preferably glass transition temperature of 55 ℃ to 70 ℃, 2,500 to 50,000 number-average molecular weight (Mn) and 10,000 to 1,000,000 weight-average molecular weight (Mw).
With respect to whole components, the alkoxide component of vibrin and acid constituents are in the ratio of mol%, that is, alkoxide component/acid constituents can be, but are not particularly limited to 45/55 to 55/45.
The charged characteristic that the quantity increase of the molecule chain end group of vibrin causes toner uprises the degree of dependence of environment.Therefore, the preferred 90mg KOH/g of acid number is following also more preferably below 50mg KOH/g.In addition, the preferred 50mg KOH/g of hydroxyl value is following also more preferably below 30mg KOH/g.
Preferably there is 50 ℃ to 75 ℃ and the more preferably glass transition temperature of 55 ℃ to 65 ℃ for the vibrin of aspect of the present invention.
Preferably have 1,500 to 50,000 and more preferably 2,000 to 20,000 number-average molecular weight (Mn) for the vibrin of aspect of the present invention.
Preferably have 6,000 to 100,000 and more preferably 10,000 to 90,000 weight-average molecular weight (Mw) for the vibrin of aspect of the present invention.
Consider band electrical stability and image reproducing, according to the present invention, the magenta toner of aspect preferably has the ratio (below, also be called " D4/D1 ") of weight average particle diameter D4 below the weight average particle diameter D4 and 1.35 of 4.0 to 9.0 μ m and number average bead diameter D1.More preferably, magenta toner has weight average particle diameter D4 and the ratio of number average bead diameter D1, the i.e. D4/D1 below the weight average particle diameter D4 and 1.30 of 4.9 to 7.5 μ m.
According to the present invention, the weight average particle diameter D4 of the magenta toner of aspect and number average bead diameter D1 change according to the method for production basis toner-particle separately.For example, in the situation of suspension polymerization, these particle mean sizes can be regulated by controlling for the preparation of the concentration of the dispersion stabilizer of aqueous medium, stirring rate between the reaction period and the mixing time between the reaction period etc.In the situation of emulsification aggregation method, the particle mean size of aggregated particle can be added and time and temperature and Agitation and mixing condition etc. during mixed flocculation agent etc. are regulated by control.In the situation of suspension comminution granulation, these particle mean sizes can be when being controlled at the solvent-laden composition of preparation bag solvent concentration, for the preparation of the concentration of the dispersion stabilizer of aqueous medium and stirring rate condition etc., regulate.
According to the present invention, the average circularity of the magenta toner of aspect is measured with streaming particle image analyser.From the viewpoint of the transfer printing that realizes significantly improving toner, magenta toner preferably has 0.950 to 0.995 and more preferably 0.960 to 0.990 average circularity.
Next, will the method that comprises the liquid developer of the water-insoluble dye composition meaned by formula (1) of aspect according to the present invention of producing be described.
Can use the magenta toner of the aspect according to the present invention as liquid developer.Below liquid developer will be described.
Liquid developer can be by the insulativity carrier fluid, dispersing or dissolving toner-particle production, and described toner-particle comprises as the dispersant resin of spreading agent and comprises the colorant by the water-insoluble dye composition of formula (1) expression.Toner-particle optionally comprises auxiliary agent, for example charge control agent and wax.Alternatively, liquid developer can be manufactured in advance concentrated toner and prepare by the two-step approach that the insulativity carrier fluid is diluted concentrated toner by comprising.
The example that is used for the dispersant resin of liquid developer comprises, but be not confined to especially the homopolymer of following monomer: styrenic monomers, styrene for example, to chlorostyrene and α-methyl styrene, acrylate monomer, methyl acrylate for example, ethyl acrylate, the acrylic acid n-propyl, lauryl acrylate, 2-EHA and vinyl cyanide, methacrylate monomers, methyl methacrylate for example, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, lauryl methacrylate, 2-Ethylhexyl Methacrylate and methacrylonitrile, vinyl ether monomers, for example vinyl methyl ether and vinyl isobutyl ether, the vinyl ketone monomer, ethenyl methyl ketone for example, vinyl ethyl ketone and vinyl isopropenyl ketone, and olefinic monomer, ethene for example, propylene and butadiene, the multipolymer that by it prepared by two or more combinations, and the potpourri of homopolymer and multipolymer.Its other example comprises the resin of epoxy resin, vibrin, urethane resin, polyamide, celluosic resin, polyether resin and non-vinyl condensation; The potpourri of these resins and above-mentioned vinylite; With the graft polymer by preparing with the vinyl monomer polymerization under existing at these.These resins can be separately or as required with two or more being used in combination.
The insulativity carrier fluid that can be used for liquid developer is not particularly limited.For example, the transfer printing of considering liquid developer can be used has 10 9the organic solvent of the low-k below the high resistivity that Ω cm is above and 3.0.The instantiation of organic solvent comprises aliphatic hydrocrbon, for example pentane, hexane, heptane, octane, nonane, decane, undecane and dodecane; Isoper H, G, K, L and M (by Exxon Chemical Co., Ltd. manufactures); With Linealene Dimer A-20 and A-20H (by Idemitsu Kosan Co., Ltd. manufactures).Organic solvent can have the boiling point of 68 ℃ to 250 ℃.These solvents can be separately or as required with two or more being used in combination, the degree do not increased with the viscosity that reaches system.
The example that can be used for the charge control agent of liquid developer comprises, but is not confined to especially, at the charge control agent used in liquid developer for development of static charge.The example comprises cobalt naphthenate, copper naphthenate, copper oleate, cobalt oleate, zirconium caprylate (zirconium octanoate), cobalt octoate (cobalt octanoate), neopelex, calcium dodecyl benzene sulfonate, soybean lecithin and aluminium octoate (aluminum octoate).
The example that can be used for the dispersion machine of liquid developer comprises, but is not confined to especially the rotational shear homogenizer, such as the medium-type dispersion machine of bowl mill, sand mill and masher etc., and high pressure subtend collision type dispersion machine.
Embodiment
Although further aspect of the present invention is described in detail as follows by embodiment and comparative example, the present invention is not limited to these embodiment.In the following description, " part " and " % " is based on quality, unless otherwise mentioned.The gained reaction product is identified by the multiple analytic approach of the equipment with as described below.That is the analytical equipment of, using is 1h-nuclear magnetic resonance spectrometer (ECA-400, by JEOL Ltd., manufactured), LC/TOF mass spectrometer (LC/MSD TOF, by Agilent Technologies, manufactured) and UV/Vis spectrophotometer (the UV-3600 spectrophotometer is manufactured by Shimadzu Corporation).About the ionization method in LC/TOF MS, adopt electro-spray ionization (ESI) method.
Produce by the following method the water-insoluble dye composition meaned by formula (1).
Synthesis example 1
The production of water-insoluble dye composition (5)
At first, by 3- acetylaminohydroxyphenylarsonic acid 2,4, the compd A (7.4g) shown in 6-trimethylaniline (7.3g) and above-mentioned synthetic schemes reacts 3 hours under zinc chloride (4.1g) exists under 150 ℃ of heating in sulfolane (20mL).Cooling gained solution, then pour 2N hydrochloric acid (50mL) into.The filtering-depositing crystal, washing, thus and provide water-insoluble dye composition (5) by the acetone crystallization.
The gained compound passes through the above-mentioned analytical equipment of use 1h-NMR spectrum, LC/TOF MS and UV/Vis spectrophotometric method are identified.Analysis result is described below.
The analysis result of water-insoluble dye composition (5)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 1):
δ[ppm]=9.72(s,2H),9.10(s,2H),8.01(d,1H,J=7.63Hz),7.60(t,1H,J=7.25Hz),7.51(t,1H,J=7.63Hz),7.18-7.08(m,7H),5.92(br,1H),2.16-1.98(m,24H)
[2] mass spectroscopy (ESI-TOF): m/z=715.2696 (M-H) -
[3] UV/Vis spectrophotometric method (λ max=530nm (CH 3oH:2.5 * 10 -5mol/L)
Notice that above-described water-insoluble dye composition (5) and water-insoluble dye composition (1) to (4) as described below and (6) have in the water that is less than 1 quality % solubleness separately to (25) and be therefore water-insoluble compound.
Synthesis example 2
The production of water-insoluble dye composition (6)
Except using 3-propionamido-2,4, the 6-trimethylaniline replaces 3- acetylaminohydroxyphenylarsonic acid 2,4,6-trimethylaniline and use amount are 3- acetylaminohydroxyphenylarsonic acid 2,4, beyond 1.3 times of the molar weight of 6-trimethylaniline, as synthesis example 1 preparation water-insoluble dye composition (6).
The analysis result of water-insoluble dye composition (6)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 2):
δ[ppm]=9.73(s,2H),9.02(s,2H),8.02(d,1H,J=7.63Hz),7.60(t,1H,J=7.63Hz),7.53(t,1H,J=8.39Hz),7.19-7.09(m,7H),5.92(br,1H),2.32(t,4H,J=7.63Hz),2.16-1.97(m,16H),1.14(t,6H,J=7.63Hz)
[2] mass spectroscopy (ESI-TOF): m/z=743.2976 (M-H) -
[3] UV/Vis spectrophotometric method (λ max=530nm (CH 3oH:2.5 * 10 -5mol/L)
Synthesis example 3
The production of water-insoluble dye composition (7)
Except using 3-butyrylamino-2,4, the 6-trimethylaniline replaces 3- acetylaminohydroxyphenylarsonic acid 2,4,6-trimethylaniline and use amount are 3- acetylaminohydroxyphenylarsonic acid 2,4, beyond 1.5 times of the molar weight of 6-trimethylaniline, as synthesis example 1 preparation water-insoluble dye composition (7).
The analysis result of water-insoluble dye composition (7)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 3):
δ[ppm]=9.73(s,2H),9.04(s,2H),8.01(d,1H,J=7.63Hz),7.61(t,1H,J=7.63Hz),7.54(t,1H,J=8.39Hz),7.19-7.09(m,7H),5.93(br,1H),2.31(t,4H,J=7.25Hz),2.16-1.98(m,18H),1.66(dd,6H,J=14.9,7.25Hz),0.96(t,6H,J=7.25Hz)
[2] mass spectroscopy (ESI-TOF): m/z=771.3306 (M-H) -
[3] UV/Vis spectrophotometric method (λ max=530nm (CH 3oH:2.5 * 10 -5mol/L)
Synthesis example 4
The production of water-insoluble dye composition (8)
Except using 3-isobutyryl amino-2,4, the 6-trimethylaniline replaces 3- acetylaminohydroxyphenylarsonic acid 2,4,6-trimethylaniline and use amount equal 3-acetylaminohydroxyphenylarsonic acid 2, beyond the molar weight of 4,6-trimethylaniline and the use amount of sulfolane double, as synthesis example 1 preparation water-insoluble dye composition (8).
The analysis result of water-insoluble dye composition (8)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 4):
δ[ppm]=9.75(s,2H),8.99(s,2H),8.01(d,1H,J=8.39Hz),7.60(t,1H,J=7.63Hz),7.51(t,1H,J=8.01Hz),7.18-7.09(m,7H),5.90(br,1H),2.65(td,2H,J=13.4,6.36Hz),2.13(m,11H),1.96(m,6H),1.15(m,13H)
[2] mass spectroscopy (ESI-TOF): m/z=771.3295 (M-H) -
[3] UV/Vis spectrophotometric method (λ max=530nm (CH 3oH:2.5 * 10 -5mol/L)
Synthesis example 5
The production of water-insoluble dye composition (10)
Except using 3-benzamido-2,4, the 6-trimethylaniline replaces 3- acetylaminohydroxyphenylarsonic acid 2,4,6-trimethylaniline and use amount are 3- acetylaminohydroxyphenylarsonic acid 2,4, beyond 1.8 times of the molar weight of 6-trimethylaniline, as synthesis example 1 preparation water-insoluble dye composition (10).
The analysis result of water-insoluble dye composition (10)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 5):
δ[ppm]=9.79(s,2H),9.66(s,2H),7.99(d,6H,J=7.63Hz),7.58-7.51(m,8H),7.18(m,6H),7.18-7.09(m,7H),5.98(br,1H),2.23-2.08(m,18H)
[2] mass spectroscopy (ESI-TOF): m/z=839.2973 (M-H) -
[3] UV/Vis spectrophotometric method (λ max=530nm (CH 3oH:2.5 * 10 -5mol/L)
Synthesis example 6
The production of water-insoluble dye composition (24)
Except using 3-(2-heptyl undecanoyl amino)-2,4, the 6-trimethylaniline replaces 3- acetylaminohydroxyphenylarsonic acid 2,4,6-trimethylaniline and use amount are 3-acetylaminohydroxyphenylarsonic acid 2, beyond 2 times of the molar weight of 4,6-trimethylaniline, as synthesis example 1 preparation water-insoluble dye composition (24).
The analysis result of water-insoluble dye composition (24)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 6):
δ[ppm]=9.72(s,2H),9.07(s,2H),8.02(d,1H,J=7.63Hz),7.61(t,1H,J=7.63Hz),7.52(t,1H,J=7.63Hz),7.11(m,7H),5.89(br,2H),3.30(t,2H,J=7.25Hz),2.69(s,3H),2.40(s,1H),2.19-2.10(m,12H),1.92(m,7H),1.60(s,3H),1.41(s,1H),1.32(s,9H),1.24(s,38H),0.84(s,12H)
[2] mass spectroscopy (ESI-TOF): m/z=1165.7665 (M+H) +
[3] UV/Vis spectrophotometric method (λ max=531nm (CH 3oH:2.5 * 10 -5mol/L)
Synthesis example 7
The production of water-insoluble dye composition (25)
Except using 3-, (2-(1,3,3-trimethyl butyl)-5,7, the 7-trimethyl) decoyl amino-2,4,6-trimethylaniline replaces 3- acetylaminohydroxyphenylarsonic acid 2,4,6-trimethylaniline and use amount are 3-acetylaminohydroxyphenylarsonic acid 2, beyond 2 times of the molar weight of 4,6-trimethylaniline, as synthesis example 1 preparation water-insoluble dye composition (25).
The analysis result of water-insoluble dye composition (25)
[1] 1h-NMR (400MHz, DMSO-d 6, 80 ℃) and (referring to Fig. 7):
δ[ppm]=9.72(s,2H),9.04(s,2H),8.02(d,1H,J=7.63Hz),7.61(t,1H,J=7.63Hz),7.52(t,1H,J=8.01Hz),7.16-7.09(m,7H),5.89(br,1H),2.20-1.99(m,18H),1.99-1.58(m,8H),1.47-1.20(m,12H),1.02-0.87(m,48H)
[2] mass spectroscopy (ESI-TOF): m/z=1165.7878 (M+H) +
[3] UV/Vis spectrophotometric method (λ max=531nm (CH 3oH:2.5 * 10 -5mol/L)
The synthesis example of other water-insoluble dye composition
Synthesize by the method according to synthesis example 1 to 7 water-insoluble dye composition (9) shown in table 1 and (11) to (23).The water-insoluble dye composition of gained passes through the above-mentioned analytical equipment of use 1h-NMR spectrum, LC/TOF MS and UV/Vis spectrophotometric method are identified.
Notice that water-insoluble dye composition (5) has the solubleness in the water that is less than 1 quality % separately to (25).
In table 1, " nC 17h 15" mean positive stearyl, and " * " means the bonding position.
[table 1]
The structure of the dye composition that table 1 is meaned by formula (1)
Figure BDA0000383456350000311
The production of toner
Produce magenta toner by the method the following describes.
The production example of particulate resin dispersion (1)
At first, mix and dissolve 82.6 parts of styrene, 9.2 parts of n-butyl acrylates, 1.3 parts of acrylic acid, 0.4 part of acrylic acid hexanediol ester and 3.2 parts of positive lauryl mercaptans.The aqueous solution of 1.5 parts of NEOGEN RK (by Dai-ichi Kogyo Seiyaku Co., Ltd. manufactures) in 150 parts of ion exchange waters added to gained solution and be scattered in wherein.Add dispersion liquid to slowly stirring under other 10 minutes the aqueous solution in 10 parts of ion exchange waters by 0.15 part of potassium persulfate.By the atmosphere in the nitrogen exchange system, then under 70 ℃, carry out emulsion polymerization 6 hours.After completing polymerization, reaction mixture is to room temperature.Ion exchange water provides the particulate resin dispersion (1) of the median particle diameter (D50) with the solid composition of 12.5 quality % and 0.2 μ m volume reference to the interpolation of reaction mixture.
The production example of coloring agent particle dispersion liquid (1)
At first, add 100 parts of water-insoluble dye compositions (5) and 15 parts of NEOGEN RK (by Dai-ichi Kogyo Seiyaku Co., Ltd. manufactures) to 885 parts of ion exchange waters.With wet type aeropulverizer (Model:JN100, by JOKOH Co., Ltd. manufactures) dispersed mixture approximately 1 hour so that coloring agent particle dispersion liquid (1) to be provided.Coloring agent particle in the coloring agent particle dispersion liquid has the median particle diameter (D50) of 0.2 μ m volume reference.The coloring agent particle dispersion liquid has the coloring agent particle content of 10 quality %.
The production example of Wax particles dispersion liquid (1)
At first, by 100 parts of ester type waxes, (peak temperature of the maximum endothermic peak of dsc measurement: 70 ℃, Mn=704) He 15 parts of NEOGEN RK (by Dai-ichi Kogyo Seiyaku Co., Ltd. manufactures) add 385 parts of ion exchange waters to.With wet type aeropulverizer (Model:JN100, by JOKOH Co., Ltd. manufactures) dispersed mixture approximately 1 hour so that Wax particles dispersion liquid (1) to be provided.Gained Wax particles dispersion liquid has the wax content of 20 quality %.
The production example of basis toner-particle (1)
At first, be mixed together and use homogenizer (Model:ULTRA-TURRAXT50 is manufactured by IKA) to disperse in 160 parts of particulate resin dispersions (1), 10 parts of coloring agent particle dispersion liquids (1), 10 parts of Wax particles dispersion liquids (1) and 0.2 part of magnesium sulphate.Under agitation add hot mixt to 65 ℃.65 ℃ of lower continuous stirring 1 hour.Observed with optical microscope, proved to have formed to there is the approximately aggregated particle of the number average bead diameter of 6.0 μ m.After adding 2.2 parts of NEOGEN RK (by Dai-ichi Kogyo Seiyaku Co., Ltd. manufactures), heating gained potpourri to 80 ℃ also stirs 120 minutes so that coalescent spherical basic toner-particle to be provided.Cooling and filtering mixt is with separating solids.Then 720 parts of ion exchange waters are added to the solid of separation.Stir the gained potpourri 60 minutes.Bag filter is containing the potpourri of basic toner-particle.Repeat identical washing and filtration until the conductivity of filtrate reaches below 150 μ S/cm.Finally, filtered with separating solids.Provide basic toner-particle (1) with the vacuum drier drying solid.
Notice that the conductivity of filtrate calculates according to the method described in Japanese Patent Laid-Open 2006-243064 communique.That is, abandon 30 parts of initial parts of filtrate.By the Temperature Setting to 25 of residue ± 0.5 ℃.Measure conductivity with conductivity meter (Model:ES-12 is manufactured by HORIBA Ltd.).The conductivity of sample is calculated by following expression formula:
Conductivity [μ S/cm]=A-B
Wherein A means the conductivity of filtrate; Mean the electrical conductivity of water for washing with B.
Note using and there is the following conductivity of 5 μ S/cm and the ion exchange water of pH7.0 ± 1.0.
The production example of basis toner-particle (2)
Except using water-insoluble dye composition (8) to replace producing the water-insoluble dye composition (5) in routine method according to coloring agent particle dispersion liquid (1), as the production example production basis toner-particle (2) of basic toner-particle (1).
The production example of coloring resin fine grained dispersion liquid (1)
In nitrogen atmosphere, 4.0mol terephthalic acid (TPA), 1.0 moles of m-phthalic acids and 0.04mol dibutyl tin oxide are added to the 2-mol oxetanes of bisphenol-A of the 2-mol propylene oxide adduct of bisphenol-A of 1.5mol and 1.8mol at the mixed solution of 1.1mol cyclohexanedimethanol and 0.62mol ethylene glycol.Under agitation at 195 ℃, make potpourri reaction 6 hours.Then add hot mixt to 240 ℃ and react 6 hours.By the pressure decreased in reaction vessel to 10.0mmHg.Under reduced pressure make potpourri react 0.5 hour to provide faint yellow amorphous linear polyester resin (1).The glass transition temperature that passes through dsc measurement of amorphous linear polyester resin (1) is 56 ℃.Amorphous linear polyester resin (1) has 11,300 weight-average molecular weight Mw, 4,400 number-average molecular weight and 2.6 Mw/Mn ratio, and described molecular weight is scaled styrene by GPC and measures.Amorphous linear polyester resin (1) has the acid number of 12mg KOH/g, and described acid number is measured according to acetone for JIS K0070-toluene mixed solution.
Next, the high temperature and high pressure dispersion machine with making by transformation dispersion machine (Model:Cavitron CD1010, by EuroTec, Ltd manufactures), disperse water-insoluble dye composition (8) and amorphous linear polyester resin (1).Particularly, 79 parts of ion exchange waters, 1 part of NEOGEN RK (by Dai-ichi KogyoSeiyaku Co., Ltd. manufactures), 1 part of water-insoluble dye composition (8) and 20 parts of amorphous linear polyester resins (1) are mixed together.Add ammonia to the pH to 8.5 of potpourri with the adjusting potpourri.The gained potpourri is by blade rotating speed and 5kg/cm at 60Hz 2pressure under the Cavitron dispersion machine of operation transformation process, use heat exchanger to add hot mixt under 140 ℃.Thus, produce the coloring resin fine grained dispersion liquid (1) with 290nm number average bead diameter.
The production example of basis toner-particle (3)
At first, be mixed together and use homogenizer (Model:ULTRA-TURRAX T50 is manufactured by IKA) to disperse in 160 parts of coloring resin fine grained dispersion liquids (1), 10 parts of Wax particles dispersion liquids (1) and 0.2 part of magnesium sulphate.Under agitation add hot mixt to 65 ℃.65 ℃ of lower continuous stirring 1 hour.Observed with optical microscope, proved to have formed to there is the approximately aggregated particle of the particle mean size of 6.0 μ m.After adding 2.2 parts of NEOGEN RK (by Dai-ichi Kogyo Seiyaku Co., Ltd. manufactures), heating gained potpourri to 80 ℃ also stirs 120 minutes so that coalescent spherical basic toner-particle to be provided.Cooling and filtering mixt is with separating solids.Then the solid separated with 720 parts of ion-exchange water washings 60 minutes.Bag filter is containing the potpourri of basic toner-particle.Repeat identical washing and filtration until the conductivity of filtrate reaches below 150 μ S/cm.Provide basic toner-particle (3) with the vacuum dryer drying solid.
The production example of toner (1) to (3)
To 100 parts of each basic toner-particles (1) to (3), add 1.00 parts with hexamethyldisilazane surface-treated hydrophobic silica powder (primary particle with 7nm number average bead diameter), 0.15 part of Titanium Dioxide Rutile Top grade fine powder (primary particle with 45nm number average bead diameter) and 0.50 part of Titanium Dioxide Rutile Top grade fine powder (primary particle with 200nm number average bead diameter).Use Henschel mixer (by Nippon Coke Engineering Co., Ltd. manufactures) that each gained potpourri is carried out to dry mixed 5 minutes to produce toner (1) to (3).
The production example that compares toner (1) to (3)
The comparative compound illustrated below using (1) to (3) replaces according to the water-insoluble dye composition (5) in the method for the production example of coloring agent particle dispersion liquid (1), as the production example comparision of production toner (1) of toner (1) to (3).
Figure BDA0000383456350000351
Comparative compound (1)
Figure BDA0000383456350000352
Comparative compound (2)
Comparative compound (3)
The production example of toner (4)
To the aqueous solution of adding 710 parts of ion exchange waters and 450 parts of 0.1mol/L tertiary sodium phosphates in the 2-L tetra-neck flasks that are equipped with high speed agitator (Model:T.K.HOMO MIXER is manufactured by PRIMIX Corporation).Revolution is set in to 12,000rpm.Add hot mixt to 60 ℃.Then little by little add the calcium chloride water of 68 parts of 1.0mol/L to potpourri, with preparation, comprise the aqueous dispersion medium as the calcium phosphate of the small water-soluble dispersion stabilizer of difficulty.
With masher (by Mitsui Mining Co., Ltd. manufacture), disperse 12 parts of water-insoluble dye compositions (8) and 120 parts of cinnamic potpourris 3 hours so that masterbatch (1) to be provided.
Figure BDA0000383456350000362
(BONTRON E-88, by Orient Chemical Industries Co., Ltd. manufactures)
10.0 parts of polar resins
(bisphenol-A of epoxy pronane modification and the condensed polymer of m-phthalic acid, Tg=65 ℃, Mw=10,000, Mn=6,000)
25.0 parts of ester type waxes
(peak temperature of the maximum endothermic peak by dsc measurement: 70 ℃, Mn=704)
0.10 part of divinyl benzene monomer
Above-mentioned formula is heated to 60 ℃, and with T.K.HOMO MIXER uniform dissolution or dispersion under 5,000rpm.Then be used as 2 of polymerization initiator by 10 parts, 2'-azo two (2,4-methyl pentane nitrile) is dissolved in wherein with the preparation polymerizable monomer composition.Polymerizable monomer composition is supplied in aqueous medium.Make the gained mixture pelleting 15 minutes when keeping revolution at 12,000rpm.Next, high speed agitator is become to the stirrer of the propeller blade be provided with.Under the mixture temperature of 60 ℃, continuous polymerization is 5 hours.The temperature of potpourri rises to 80 ℃.Continue polymerization 8 hours.After completing polyreaction, under 80 ℃, under decompression, remove residual monomer.The temperature to 30 of cooling mixture is ℃ to provide the polymer fine particles dispersion liquid.
The polymer fine particles dispersion liquid is transferred to washing container.Under agitation watery hydrochloric acid is added to wherein to regulate pH to 1.5.Continue to stir 2 hours.Carry out Separation of Solid and Liquid to provide polymer fine particles with filtrator.The again dispersion of repeating polymer fine grained in water and Separation of Solid and Liquid are until fully remove the phosphoric acid that comprises calcium phosphate and the compound of calcium.The polymer fine particles that then will finally carry out Separation of Solid and Liquid is fully dry to provide basic toner-particle (4) with exsiccator.
Carry out outside identical in the production example with toner (1) for basic toner-particle (4) additional, produce thus toner (4).
The production example of toner (5)
Except using water-insoluble dye composition (25) to replace water-insoluble dye composition (8), as the production example of toner (4) is produced toner (5).
The production example of toner (6)
Except adding 1.2 parts of n-butyl alcohols in masterbatch, as the production example of toner (5) is produced toner (6).
The production example of toner (7)
At first, use Henschel mixer (Model:FM-75J, by Mitsui Mining Co., Ltd manufactures) by 100 parts of resin glue (vibrin, Tg:55 ℃, acid number: 20mg KOH/g, hydroxyl value: 16mg KOH/g, molecular weight: Mp4500, Mn:2,300, Mw:38,000), 5 parts of water-insoluble dye compositions (23), 0.5 part 3,5-di-tert-butyl salicylic acid aluminium compound and 5 parts of paraffin (temperature of maximum endothermic peak: 78 ℃) mix well.Mediate potpourri with being set in 130 ℃ of Dual-screw kneaders (Model:PCM-45 is manufactured by Ikegai Ironworks Corp.) with 60kg/hr supply rate (temperature of the potpourri of mediating during injection is approximately 150 ℃).The potpourri of cooling kneading, use the hammer-mill coarse crushing, and under the supply rate of 20kg/hr, fine powder is broken with mechanical type grinding machine (T-250, by Turbo Kogyo Co., Ltd manufactures).
The toner-particle that utilizes Coanda effect to come the classification gained to pulverize by cutting apart grader (multi-division classifier), produces basic toner-particle (7) thus.
Carry out outside identical in the production example with toner (1) for basic toner-particle (7) additional, produce thus toner (7).
Measure
The physical property of measurement gained toner as described below.
The weight average particle diameter D4 of toner and number average bead diameter 1
Measure number average bead diameter (D1) and the weight average particle diameter (D4) of above-mentioned toner-particle according to the Coulter method by particle size distribution analysis.With Coulter Counter TA-II or Coulter MultiSizer II (by Beckman Coulter, Inc. manufactures), as measuring equipment, according to the operation manual of described equipment, measured.Can use the aqueous solution of about 1% sodium chloride as electrolyte solution, prepared by 1 grade sodium chloride by described aqueous solution.For example, ISOTON-II (by Beckman Coulter, Inc. manufacture) be obtained commercially and can use.Concrete measuring method is as follows: at first, add 0.1 to 5mL surfactant (for example, alkyl benzene sulfonate) to 100 to 150mL electrolyte solutions as spreading agent.Then measuring sample (toner) by 2 to 20mg adds to wherein.The electrolyte solution of the sample that comprises suspension carries out dispersion treatment approximately 1 to approximately 3 minutes with ultrasonic dispersing machine.The volume and the quantity use that have separately the toner-particle of size more than 2.00 μ m in the gained dispersion liquid are equipped with the measuring equipment in 100-μ m hole to measure, to calculate volume distributed median and the distributed number of toner-particle.Measure number average bead diameter (D1), weight average particle diameter (D4) (intermediate value of each passage is got the typical value of doing each passage) and D4/D1.
As above-mentioned passage, use following 13 passages: 2.00 to 2.52 μ m, 2.52 to 3.17 μ m, 3.17 to 4.00 μ m, 4.00 to 5.04 μ m, 5.04 to 6.35 μ m, 6.35 to 8.00 μ m, 8.00 to 10.08 μ m, 10.08 to 12.70 μ m, 12.70 to 16.00 μ m, 16.00 to 20.20 μ m, 20.20 to 25.40 μ m, 25.40 to 32.00 μ m, and 32.00 to 40.30 μ m.
The measurement of the average circularity of toner
With streaming particle image analyser " FPIA-2100 " (being manufactured by Sysmex Corporation), measured.Average circularity is calculated by following expression formula.
[mathematical expression 1]
Figure BDA0000383456350000391
[mathematical expression 2]
Figure BDA0000383456350000392
Herein, term " projected area of particle " is defined as the area of the binary image of toner-particle.Term " girth of the projects images of particle " is defined as by the length of the outline line of the marginal point acquisition of the image of connection toner-particle.Circularity is as the index of granular concave degree.When having circularity when spherical completely, particle is expressed as 1.000.The increase of the complicacy of surface configuration reduces circularity.
Estimate
The evaluation of magenta toner is as described below.Table 2 illustrates evaluation result.
The brightness of image sample and the evaluation of saturation degree
Use the gained toner to form image sample.The brightness of assess sample and saturation degree.For the movement images characteristic, use the reforming equipment of LBP-5300 (being manufactured by CANON KABUSHIKI KAISHA) to carry out the image output test as image forming apparatus.With the stainless steel scraper plate with thering are 8 μ m thickness replace the developing blade in handle box and can apply for be applied to as the development bias voltage (developing bias) of the developer roll of toner supporting mass-the such mode of scraper plate bias voltage of 200V transformed.
For each gained image sample, with reflection of the concentration (Model:SpectroLino is manufactured by GretagMacbeth), measure the colourity (L*, a*, b*) in the L*a*b* color system.
In the L*a*b* space, the chromaticity coordinates that means the magenta of Japan Color2001 is defined as to X (L 1, a 1, b 1).In the L*a*b* space, will comprise the plane of L* axle and coordinate X and the coordinate of the intersection point of the a*b* curve of the image sample that obtains by colour measurement is defined as Y (L 2, a 2, b 2).A plurality of image samples that have different toner adhesion amounts by formation obtain the a*b* curve.Calculating is at the c* of intersection point Y value [=c 2={ (a 2 2+ b 2 2) 1/2] and at the c* of coordinate X value [=c 1={ (a 1 2+ b 1 2) 1/2] difference △ c (=c 2-c 1).Calculate L* the value (=L of intersection point Y 2) and at the L* of coordinate X value (=L 1) difference △ L (=L 2-L 1).
Estimate brightness and saturation degree based on following evaluation criterion.
A: △ c is more than 0, and △ L is more than 0;
B: △ c is more than-5, and △ L is more than-5, gets rid of the situation of above-mentioned A level; With
C: △ c is less than-5, or △ L is less than-5.
△ c be more than-5 and △ L in situation more than-5, sample is evaluated as and has gratifying brightness and saturation degree.
Sunproof evaluation
Image sample is put into to Atlas Weather-Ometer Ci4000 (from Toyo Seiki Seisaku-sho, Ltd.) and exposed 60 hours.In this case, measuring condition is as follows: blackboard temperature: 50 ℃, and room temperature: 40 ℃, relative humidity: 70%, and irradiance: 0.39W/m 2(340nm).
By the colourity (L*, a*, b*) of reflection of the concentration (Model:SpectroLino is manufactured by GretagMacbeth) in exposure test fore-and-aft survey L*a*b* color system.The measurement of color-based characteristic is calculated aberration (△ E) by following formula:
Aberration (△ E)={ (a* after the a*-test before test) 2+ (b* after the b*-test before test) 2+ (L* after the L*-test before test) 2} 1/2
After 60 hours, △ E is less than in 10 situation, and sample is evaluated as and has gratifying photostability.
Table 2 illustrates toner (1) to (7) and the evaluation result of toner (1) to (3) relatively of aspect according to the present invention of producing in the production example.
[table 2]
Table 2 evaluation result
Figure BDA0000383456350000411
As shown in table 2, in using the toner of comparative compound 1, although brightness is satisfactory, do not provide well balanced between saturation degree and photostability.In each toner that uses comparative compound 2 and 3, although photostability is satisfactory, brightness and saturation degree deficiency.On the contrary, there is well balanced as between the spectral reflection characteristic such as high brightness and saturation degree and high-light-fastness by each toner that uses the dye composition production meaned by formula (1).
Although the reference example embodiment has been described the present invention, should understand the present invention and be not limited to disclosed exemplary.The scope of following claims meets the widest explanation in order to comprise all these type of improvement and equivalent structure and function.
The application requires the rights and interests of No. 2011-059554th, the Japanese patent application submitted on March 17th, 2011, at this by its whole introducing for your guidance.
utilizability on industry
Aspect of the present invention provides the magenta toner had as spectral reflection characteristic and high-light-fastness such as high-color rendering and the transparencys.According to the present invention, the magenta toner of aspect is for using the image forming apparatus of electrophotography, for the toner demonstration of Electronic Paper and the toner that is used to form the circuit design of being made by numeral.

Claims (7)

1. a magenta toner, it comprises:
The water-insoluble dye composition meaned by formula (1); And resin glue:
Formula (1)
Figure FDA0000383456340000011
In its Chinese style (1), R 1, R 5, R 6and R 10mean independently of one another alkyl; R 3and R 8mean independently of one another hydrogen atom, alkyl, alkoxy or aryloxy group; And R 2, R 4, R 7and R 9mean independently of one another hydrogen atom or the acylamino-meaned by formula (2), condition is R 2, R 4, R 7and R 9one of at least mean the acylamino-meaned by formula (2):
Formula (2)
Figure FDA0000383456340000012
In its Chinese style (2), R 11mean alkyl, naphthenic base, aryl, aralkyl, thiazolinyl or heterocyclic radical; And * means the bonding position.
2. magenta toner according to claim 1, the R in its Chinese style (2) 11mean alkyl or aryl.
3. magenta toner according to claim 1, the R in its Chinese style (2) 11mean straight chained alkyl.
4. magenta toner according to claim 1, in its Chinese style (1), R 1and R 6mean identical substituting group, R 2and R 7mean identical substituting group, R 3and R 8mean identical substituting group, R 4and R 9mean identical substituting group, and R 5and R 10mean identical substituting group.
5. magenta toner according to claim 1, wherein said magenta toner comprises
Basis toner-particle and the lip-deep external additive that is positioned at described basic toner-particle, each self-contained resin glue of described basic toner-particle, wax and colorant.
6. magenta toner according to claim 5, wherein said basic toner-particle is produced by suspension polymerization.
7. magenta toner according to claim 5, wherein said basic toner-particle is produced by the emulsification aggregation method.
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Publication number Priority date Publication date Assignee Title
US9098004B2 (en) 2012-12-27 2015-08-04 Kao Corporation Liquid developer
EP2781514B1 (en) * 2013-03-21 2015-11-18 Canon Kabushiki Kaisha Compound, ink, ink cartridge and ink jet recording method
JP2017090544A (en) * 2015-11-04 2017-05-25 花王株式会社 Electrophotographic toner

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1129817A (en) * 1994-10-05 1996-08-28 佳能株式会社 Two-component type developer, developing method and image forming method
US20030019392A1 (en) * 2000-02-21 2003-01-30 Shigemi Wakabayashi Water-based ink
US20050188894A1 (en) * 2004-02-27 2005-09-01 Canon Kabushiki Kaisha Colorant material, and water dispersion, ink, ink tank, recording unit, recording apparatus and recording method using the same
JP2005250000A (en) * 2004-03-03 2005-09-15 Canon Inc Magenta toner

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1435776A (en) * 1973-09-06 1976-05-12 Ici Ltd Reactive xanthenium dyestuffs
DE3714289A1 (en) * 1987-04-29 1988-11-10 Bayer Ag FANAL PIGMENTS OF RING-CLOSED INDAMINE AND DIPHENYLMETHANE DYES CONTAINING DRY TONERS
JP3743052B2 (en) * 1996-03-08 2006-02-08 コニカミノルタホールディングス株式会社 Inkjet recording liquid
JP3897533B2 (en) * 2000-02-21 2007-03-28 花王株式会社 Water-based ink
WO2004101688A1 (en) * 2003-05-16 2004-11-25 Canon Kabushiki Kaisha Novel coloring compound and recording material using the same
JP4621040B2 (en) * 2004-02-27 2011-01-26 キヤノン株式会社 Dye body, aqueous dispersion, ink, ink tank, recording unit, recording apparatus and recording method using the same
US7223508B2 (en) * 2004-03-22 2007-05-29 Konica Minolta Holdings, Inc. Toner for developing electrostatic image, method for producing the toner and image forming method
US20080299477A1 (en) * 2007-05-28 2008-12-04 Konica Minolta Business Technologies, Inc. Electrophotographic toner and method of manufacturing electrophotographic toner

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1129817A (en) * 1994-10-05 1996-08-28 佳能株式会社 Two-component type developer, developing method and image forming method
US20030019392A1 (en) * 2000-02-21 2003-01-30 Shigemi Wakabayashi Water-based ink
US20050188894A1 (en) * 2004-02-27 2005-09-01 Canon Kabushiki Kaisha Colorant material, and water dispersion, ink, ink tank, recording unit, recording apparatus and recording method using the same
JP2005250000A (en) * 2004-03-03 2005-09-15 Canon Inc Magenta toner

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106061749A (en) * 2014-02-28 2016-10-26 佳能株式会社 Thermal transfer recording sheet
CN106061749B (en) * 2014-02-28 2018-12-25 佳能株式会社 Heat-sensitive transfer recording piece

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